JP5537866B2 - Thermal catalyst coating - Google Patents

Description

  The present invention relates to a thermocatalytically active coating, that is, a substrate that has been at least partially coated with a thermocatalytically active coating, a method for producing a thermally catalytically active substrate surface, and the use of the method.

  Thermal catalyst layers and thermal catalyst surfaces are well known and are used to purify automobile exhaust gases and assist in self-cleaning in a baking oven. As the above-described coating, a precious metal coating such as platinum or an enamel coating containing a transition metal is generally used. The bakery open is provided with a closable cooking space defined by a baking oven indirect heating chamber. During the use of the oven, the side walls of this cooking space are frequently soiled, for example, with oil splashing and roasting during roasting, similar to the inspection glass. Since such dirt is usually inevitable, many attempts have been made to facilitate cleaning of such cooking spaces. In the present application, catalyst cleaning and pyrolytic cleaning are distinguished from each other throughout.

  In the pyrolysis cleaning of the baking oven, a heater, which is an attached device, is operated, and the dirt is completely burned out by this heater at 500 ° C. for about 2 hours. However, this pyrolytic cleaning has a problem that it is complicated because a high temperature must be used, and energy cost is required each time.

  A combustion chamber cleaning inspection glass such as a flue stove is similarly complicated in arrangement. In addition, the inspection glass can be cleaned only by the pyrolysis method. However, in the manufacture of flue stoves, the inspection window is required not to be hot from the viewpoint of efficiency and safety. Therefore, it does not reach the temperature of 500 ° C. or more which is usually required in pyrolysis cleaning, or at least the stove. It does not reach the surface.

  In the case of catalyst cleaning, dirt and exhaust gas are decomposed, oxidized and / or burned by the action of the catalyst and / or the oxidizing agent even at a low temperature, that is, a temperature clearly lower than 500 ° C. Therefore, the catalyst system is preferable to the pyrolysis system from the viewpoint of cost. In the case of a catalyst cleaning system, a catalytically active coating is usually applied to the surface to be cleaned.

  The catalyst layer in the baking oven is known as a coating in the baking oven indirect heating chamber. DE 10150825 A1 describes a highly porous coating consisting of porous particles and a binder matrix. The purpose of such a thick coating is to diffuse and absorb fat in the coating layer. Catalytic decomposition proceeds in the presence of transition metal particles, and it is possible to initiate decomposition even at temperatures below 300 ° C. These prior art coatings are not transparent. Therefore, coating of self-cleaning catalytically active coatings on baking oven inspection glass has been excluded to date. Therefore, the baking oven glass still had to be cleaned with an abrasive or other chemical cleaner.

  US 7,297,656 B2 describes a catalyst layer for decomposing diesel oil soot. This coating layer contains doped platinate. This patent describes doping of platinate with lithium, which states that this doping reduces the onset temperature of platinum catalysis from 392 ° C. to 366 ° C. In this patent, the presence of platinum is an essential requirement. Therefore, it is not obvious to those skilled in the art that the layer containing no platinum and containing lithium exhibits a remarkable activity.

EP 0 645 173 B1 describes a catalyst comprising a combination of lithium and platinum or palladium. Lithium is intended to suppress the toxic reaction of platinum or palladium. Lithium is produced in the strongest possible Al ₂ O ₃ support in the composite, and the support is treated with platinum or palladium, or other metal ions. This type of catalyst is used for exhaust gas purification. According to this patent, it is not obvious to those skilled in the art that lithium containing no platinum or other composites of the above-mentioned support material is active.

  EP14102060B1 describes the use of alkali metals, preferably potash, in spark ignition internal combustion engines. Here, the support material is impregnated in an aqueous potassium solution. This patent does not mention that transparent products are possible. The patent also states that catalysis is obtained primarily by the redox ability of the support material and that the catalytic effect is further enhanced by alkali metals, in this case mainly potash. Lithium is not described as a single active ingredient.

  Another type of diesel soot filter is described in EP 0105113B1. In one embodiment of this patent, an aqueous LiOH solution is poured over the filter. The ignition temperature is 467 ° C. Given the high ignition temperature disclosed in this patent publication, it may not be assumed that the selected composition can be used in the present invention. Furthermore, LiOH is highly alkaline, highly reactive, and corrosive to various substrate materials such as glass, glass ceramics, metals and certain plastics.

  The catalyst layer is also used for deodorization.

  EP 1165153 B1 describes a silicate glass to which transition metal particles are added in order to obtain catalytic activity. Although this description is optional, there is also a description related to the addition of glass-forming elements, and lithium is listed as one of these elements. Since it is known that lithium-containing glass that has not been properly surface-finished has no catalytic activity, it is not obvious that lithium in this case has catalytic activity.

  The use of noble metals increases costs and is often disadvantageous because the coating of transition metal compounds produces a unique color in the coating layer. Furthermore, in order to obtain a sufficient decomposition reaction rate, a material having an extremely large surface area is often required.

  Therefore, there is a need for a transparent surface that is more durable, has a longer life, and is self-cleanable. A surface with such characteristics is particularly advantageous, for example, in flue stoves or other combustion chambers in cooking utensils, roasting utensils, baking utensils, grill utensils and in flue gas purification components such as odor reducing components. Used.

  Accordingly, the present invention preferably aims to provide a thermal catalyst coating that is not only fast and thin, but also has no inherent coloration at low temperatures below 350 ° C. It is another object of the present invention to use only a lithium precursor that does not affect the substrate, does not corrode the substrate surface, and has a pH of 11 or less.

  The present invention further provides a substrate having at least partially a thermocatalytically active surface on which soot and other organic or oxidizable compounds are allowed to reach a temperature that is possible when using known substrates. Another object of the present invention is to provide a substrate capable of catalytic combustion at a considerably low temperature.

  It is another object of the present invention to provide a method for producing the substrate provided with a thermal catalyst coating.

  Surprisingly, by using a coating containing at least one lithium compound, for example, decomposition reaction of organic matter such as soot burning on a thermocatalytic coating, or food stains, ie self of hydrogen compounds, carbohydrates, proteins, fats, etc. It has been found that the temperature at which cleaning proceeds can be significantly reduced. Further surprisingly, the coating also shows catalytic activity for the oxidation of carbon monoxide in the flue gas stream.

  According to the invention, the object is to include in the coating according to the invention at least one lithium compound in an amount corresponding to 2% by weight or more as lithium ions in a weight ratio to the total weight of the coating. Achieved by:

  Furthermore, the above object is achieved by a method for producing a substrate comprising the steps of preparing a coating composition, treating the coating composition onto a substrate, and drying the coated substrate.

  The term “lithium compound” used in the present application includes all ionic compounds having a pH of 11 or less and containing at least one lithium ion. As these lithium compounds, for example, in addition to known inorganic lithium salts such as lithium phosphate, lithium nitride, lithium halide and lithium sulfate, organic lithium-containing compounds such as lithium acetate, lithium succinate tetrahydrate, lithium propionate and Examples include lithium derivatives of carboxylic acids, and mixed oxides containing lithium, such as any lithium ion-containing compound produced in the thermal decomposition of an organolithium compound or produced by reactive conversion of metallic lithium.

  Apart from the unavoidable impurities that occur, for example, in the raw materials used or as a result of the preparation, the coating preferably does not contain any Li2O and / or LiOH. In a humid atmosphere, Li2O is easily converted to LiOH, which causes the surface to exhibit very high alkalinity, resulting in the possibility of violating the substrate. Therefore, Li2O must be kept in a clean and dry atmosphere.

  In the present invention, the pH is based on a safety data sheet issued by Merck Chemicals (Merck KGaA, Darmstadt, Germany), and is usually a pH at a concentration of 50 g / liter of water at 20 ° C. However, it has been reported that if the solubility of the material is too low, for example at a concentration of 5 g / liter of water and at higher temperatures the pH will be much smaller.

  The lithium compound is essentially the thermocatalytically active part of the coating.

  In the present invention, the term “thermal catalyst” or “thermocatalytic” means that the activation energy of the reaction is lowered by lowering the reaction temperature by using the shaped body according to the invention.

  However, the lithium compound is an amorphous inorganic compound and / or a crystalline inorganic compound, especially Si, B, Ge, Bi, Al, Na, Li, K, P, Mg, Ca, Sr, Ba, Mn, Ni, Oxides and / or nitrides and / or carbides of Co, Cr, V, Sn, Zn, In, Fe, Ti, Zr, Hf, Y, Nb, Ce, Gd, La, Sm, Ta, and W, and Or fluoride may be sufficient.

  Also, the coating includes impurities, C, Si, B, Ge, Bi, Al, Na, K, P, Mg, Ca, Sr, Ba, Mn, Ni, Co, Cr, V, Sn, Zn, In , Fe, Ti, Zr, Hf, Y, Nb, Ce, Gd, La, Sm, Ta, W, etc. or dopant components consisting of noble metals such as Pt, Rh, Pd, Ru, Au, Ag It may be. The dopant component is preferably added to a content of less than 2% by weight.

  In the present invention, the lithium compound can be present without using a binding substrate or in a state of being bound in the substrate. Accordingly, it is possible to dissolve lithium compounds or to treat the compounds on a substrate. In the present invention, any common solvent such as water, alcohols, ketones, acetones, acetylacetonate, ethyl acetate, polyhydric alcohols, and mixed solvents thereof can be used.

  In a preferred embodiment, a coating comprising a lithium compound according to the present invention and a binding substrate is produced. The binding substrate may consist of an inorganic substrate, an organic substrate, or a mixture thereof.

  The above-mentioned inorganic substrate means compounds such as glass, glass solder, and sol / gel substrate. Such inorganic substrates preferably include silicon oxide, titanium oxide, zirconium oxide, aluminum oxide, cerium oxide, iron oxide, tin oxide, boron oxide. In the present invention, the substrate may comprise a mixture of the substrate components described above.

  In the present invention, an inorganic sol-gel substrate is preferably used. The generation of such sol-gel systems is known to those skilled in the art. In the present invention, it is preferable that a thin transparent gel film or gel layer is formed after drying or heat treatment.

  The sol-gel substrate is water, an organic solvent, or water and alcohols, polyhydric alcohols, acetones, ketones, acetylacetonate, ethyl acetate, 2-butoxyethanol, 1-propanol, 2-propanol, Produced by acid-catalyzed or base-catalyzed hydrolysis in a water / organic solvent mixture such as methanol, ethanol, and at least one solvent selected from other solvents known to those skilled in the art. These sols are usually clear and stable solutions containing solids in the range of about 1% to about 40% by weight. The sol-gel layer produced is preferably, for example, silicon oxide, germanium oxide, titanium oxide, zirconium oxide, aluminum oxide, cerium oxide, boron oxide, iron oxide, tin oxide, or a mixture thereof. It consists of metalloid oxides or metal oxides.

  In the present invention, the organic substrate means an organic compound which may be composed of wax, polymer, surfactant, carboxylic acid, fatty acid, oil, resin, silicone resin, or a mixture thereof. This organic substrate is used for the purpose of fixing the lithium compound to the substrate. In the present invention, the polymer means a carbonaceous polymer. Preferred polymers include silicones and silicone resins, as well as polymers that thermally decompose residue-free compounds such as polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, and cellulose.

  In yet another embodiment of the invention, preferably a mixture comprising at least one thickener selected from xanthan gum, glycerol, polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, cellulose, cellulose derivatives, and mixtures thereof is used. .

  It has been found that by using the thickener, it is possible to efficiently produce a paste particularly used for producing a thermal catalyst layer.

  The coating containing the thickener has the advantage of being easy for the end user to handle and easily polishing the substrate surface using a conventional cloth. These thickeners are not toxic and do not break down and remain.

  Of course, the features described above and further described below are used not only in the combination of the features described in each case, but also in other combinations or alone, without departing from the scope of the invention. It is possible.

  The viscosity of the coating is selected to be in the range of the liquid or paste, that is, in the range of 0.5 mPa · s to 106 mPa · s. The desired viscosity can be obtained by appropriate choice of solvent, thickener or substrate and by adding particles or insoluble components. In this case, a particularly preferred particle size is in the range of 2 to 200 nm. Particles can be used to thicken the coating solution, and other particles such as coating solution particles having functional characteristics such as reflection characteristics at a specific wavelength in the infrared or ultraviolet range, coloring characteristics, bactericidal characteristics, etc. It is also possible to add particles that can further increase the catalytic activity.

  In the present invention, the thermocatalytic reaction occurs within a temperature range of 100 to 600 ° C, preferably 200 to 400 ° C, particularly preferably 300 to 350 ° C.

  In order to further increase the utility value of the thermal catalyst self-cleaning surface, it is necessary to provide the substrate with a surface on which the catalytic decomposition proceeds even at a low temperature. Furthermore, the surface design must be performed so that the substrate is not damaged by the heating cycle.

  In such a case, the thermocatalytic active surface according to the present invention can be formed as a continuous layer on the entire surface of the substrate or a part thereof, or as a small distribution of agglomerates. It will be appreciated by those skilled in the art that when present as a discontinuous layer, the lithium concentration can only be obtained in the form of dots.

  The substrate in the present invention can be constructed using various materials, but the material must be heat resistant to 350 ° C. As a substrate material, for example, any glass ceramics such as Seran (registered trademark), Robax (registered trademark), Zerodur (registered trademark), Borofloat (registered trademark), Duran (registered trademark), Fiorax (registered trademark) ) And the like, and glass, ceramics, metals, and certain high temperature plastics can be selected. Obviously, the substrate surface can be modified with, for example, enamel, decoration, heat reflecting layer, antireflection surface, porous substrate such as baked glass or baked glass ceramic layer, adhesion promoting layer, and barrier layer. It is. Such a change can be made at least partially on one side or both sides of the substrate, and may be a multilayer structure if appropriate. Obviously, it is also possible to apply the desired coloration, image or structure to the coating part.

  Further, the substrate can be formed into various shapes. For example, the substrate may be shaped into a flat or three-dimensional plate, perforated filter, fiber, molded article, or other special shape, such as a powder. For coated parts or products, there is no particular limitation on the shape of the present invention as well as on the material, so it can be flat, circular, curved, large, small, etc. It is.

  The surface of the substrate according to the present invention may have a porous structure or a non-porous structure. In the case of a porous structure, the porosity is 2 to 70%, preferably 5 to 50%.

  The lithium-containing surface can be produced as a component integrated with the substrate, but may be configured to exist as a coating on the substrate. The lithium compound may be a single salt or may be composed of other components as a mixed salt. The lithium compound may be present as a crystalline or amorphous layer, or as a particle, or may be encapsulated in a substrate, or may be present in other systems such as zeolite. In this case, it is only necessary to have access to a part of the lithium compound on the surface. If the thermocatalytically active surface is formed by a coating, the coating can be processed directly onto the substrate, or other functional layers such as infrared reflective layers, adhesion promoting layers, or diffusion of lithium into the substrate. It is also possible to provide a barrier layer between the substrate and the substrate surface that prevents or at least retards.

  The thermocatalytically active surface according to the present invention can be formed directly during the production of the substrate or can be processed into the substrate by methods known to those skilled in the art. Examples of the method further include liquid coating methods such as spraying, overflow, pouring, or immersion treatment, and roller and screen printing using a lithium compound solution, CVD, and PVD treatment. As another possibility for manufacturing the substrate according to the present invention, a method in which a lithium compound or lithium ion is contained in the substrate material and can be accessed by surface treatment such as etching treatment can be used.

  In yet another embodiment, the lithium compound is bound to the substrate, preferably by heat treatment, when not included in the substrate. Certain portions of such lithium compounds may be molten. There is a possibility that ion exchange proceeds between the substrate and lithium at a relatively high temperature, that is, a temperature higher than 300 ° C. Preferably, in an ion exchange reaction in glass, fired glass, and ceramics, for example, hydrogen ions generated from the substrate are exchanged for lithium ions. In this case, the ion exchange can proceed during the glass production process, such as during the float process or glass forming, or heat treatment downstream. In this case, the tempering process is preferably performed because an additional processing step becomes unnecessary and the required energy is efficiently used. As described in DE102006056088A1, in the case of glass ceramics, the ion-exchanged lithium ions are incorporated into the crystalline phase of the glass ceramic during the ceramization process, so that the catalytic reaction is not sufficiently performed. Implementation is less preferred.

  In a preferred method, the surface is formed by treating a paste-like lithium compound. In this case, the paste is particularly easy to handle, for example for cleaning a substrate that has already been soiled, for imparting a thermal catalytic function to the substrate, or for replenishing a pre-existing thermal catalytic function. There is an advantage that the end user can perform desired processing on the substrate at home as needed.

  In another preferred embodiment, the coating is performed by a sol-gel process. The advantage of the sol-gel method is that by using the sol-gel method, it is preferably very porous, which makes it possible to create a catalytically highly active system. Other possible coating methods include PVD and CVD methods.

  A substrate containing a thermocatalytically active surface in the form of a coating is prepared, for example, by treating the coating composition or solution onto the substrate, then drying the treated coating composition, etc., and further processing if necessary. Is possible. The drying temperature in this case is in the range of 20 to 750 ° C., preferably 20 to 500 ° C., particularly preferably 20 to 450 ° C. The substrate can be easily produced by such means.

  In yet another embodiment of the above method, the thickness of the coating is in the range of 1 nm to 1 μm, preferably 5 nm to 350 nm, particularly preferably 10 nm to 300 nm or 200 nm.

  By using a coating having such a thickness, a substrate having a non-uniform thickness that impairs other properties, for example, the aesthetics of the substrate, is not formed, and the substrate is stable over a long period of time. It is possible to produce a thermocatalytically active coating.

  In yet another embodiment of the above method, a barrier layer is arranged between the substrate and the coating.

  By providing this barrier layer, it is possible to prevent diffusion of lithium ions from the thermal catalyst active surface into the substrate. Such a system makes it possible to maintain the lithium ion content, and thus the thermal catalytic activity of the thermal catalytic active surface, over a long period of time. Further, as a result, it is possible to prevent the substrate from being damaged by the gas released during the catalytic decomposition. An example of such a gas is, for example, a sulfur-containing gas, and the stability of the glass substrate is impaired by this gas.

Examples of such a barrier layer include a layer made of SiO ₂ , SnO ₂ , Al ₂ O ₃ , ZrO ₂ and TiO ₂ , and a layer made of a mixture of these oxides.

  In yet another embodiment of the invention, both the substrate and the surface are transparent. Also preferably, both the substrate and the surface are colorless.

  In such a configuration, it is possible to produce a transparent and colorless inspection window using the substrate according to the present invention. For example, the inspection window is self-cleaning even under the influence of heat generation in the combustion chamber, It is possible to ensure that the inside can be seen.

  In the present invention, the term “combustion chamber” includes any chamber in which combustion of an oxidizing substance such as a carbon-containing substance, a carbohydrate-containing substance, or a nitrogen-containing substance proceeds. Combustion chambers include combustion chambers of internal combustion engines, industrially used combustion chambers, and open or closed flue or flue stoves used in the home. However, the term “combustion chamber” also includes other chambers, ie cooking utensils, roasting utensils, grill utensils, or baking ovens where carbon-containing or carbohydrate-containing materials are exposed to high temperatures.

  In yet another embodiment of the present invention, an inspection window using the substrate according to the present invention is installed in the combustion chamber, and a thermal catalyst active surface is formed on a side surface of the inspection window facing the combustion chamber.

  By using the substrate according to the present invention as an inspection window for a combustion chamber arranged so that the substrate surface faces the combustion chamber, it becomes possible to effectively prevent the inspection window from being soiled. Is not required to be frequently cleaned, and it is ensured that the combustion chamber can be observed over a long period of time.

  In still another embodiment of the present invention, an infrared reflection layer is further arranged on the substrate.

  In this case, the infrared reflection layer may be disposed directly below the thermal catalyst active surface, or may be disposed on the side surface of the substrate far from the thermal catalyst active surface when the substrate transmits infrared rays. . By providing such an infrared reflection layer, infrared rays that enter through the thermal catalyst active surface are reflected by the infrared reflection layer and pass through the thermal catalyst active surface again. As a result, the temperature of the thermal catalyst active surface rises, so that the thermal catalytic decomposition activity is greatly enhanced.

Examples of materials used for the infrared reflecting layer include SnO ₂ and indium-tin oxide, aluminum-zinc oxide, and noble metals.

  In yet another embodiment of the invention, the combustion chamber is provided with a flue gas outlet and a substrate according to the invention is arranged in the area of this flue gas outlet.

  Such a flue gas outlet may be, for example, a chimney or a baking oven, or an exhaust port of an internal combustion engine. In such a case, the substrate according to the invention can be placed inside the combustion chamber itself, in the middle between the combustion chamber and the roadside gas outlet, or in the top of the flue gas outlet.

  By placing the substrate according to the invention in the flue gas outlet part, the amount of soot, fines and gases such as nitrogen oxides, carbon monoxide, sulfur gases, etc. released from the combustion chamber into the environment is greatly increased. Such a configuration greatly increases the “kindness” of the combustion chamber to the environment.

  By using the substrate according to the present invention in the soot catalytic combustion process, it is possible to greatly reduce the progress temperature of soot combustion using the catalyst, so this process proceeds at a conventional temperature in the combustion chamber according to the present invention. As a result, the need for additional heating for soot combustion is eliminated.

  In the present invention, “soot” means any substance lump that is particulate and consists mostly of carbon. This “soot” includes not only products produced by incomplete combustion of carbon-containing materials and carbohydrate-containing materials, but also carbon-containing lumps produced, for example, by heat treatment of carbohydrates. In addition to carbon, the “soot” includes other components such as unburned carbohydrates, sulfur compounds, nitrogen compounds, and metals and metal compounds.

  In this regard, the “mochi” further adheres to the surface of the carbonized food residue, i.e. cooking utensils, roasting utensils, baking utensils, grill utensils, and at least in part into the self-cleaning coating substrate. Alternatively, it refers to food residues and mixtures that may have entered the pores present in the substrate. These food residues and the like may be liquids / oils, aqueous phases (salt and sugar solutions) and carbohydrates, or mixed proteins at the operating temperature. In particular, impurities include, for example, sunflower oil, soybean oil, vegetable oil, olive oil and the like, and tomato sauce, cheese, fruit juice, and milk.

The coating, surface, and substrate according to the present invention can be used in the following applications. That is,
As a component in a chimney or flue stove, preferably a flue inspection window, chimney inner lining material, chimney flue pipe lining, chimney filter,
Components in or on the heating system, preferably heating system inner lining, flue tube lining, flue tube filters, roasting equipment, baking equipment, grilling equipment or components in or above, preferably cooking surface, inspection glass , Inner lining, exhaust pipe lining, exhaust pipe filter, deep fryer,
Cooking utensils, microwave ovens, baking sheets, baking molds, mesh bread baking grids, barbecue sets, industrial automatic bread baking machines, particularly preferably components in or on the pyrolysis furnace, components on the steam ventilation fan hood, Preferably filter material,
Components on the solar thermal system, preferably the receiver tube, components on the reactor, preferably inspection windows, filter systems,
Components on or in the combustion system, waste incineration plant, crematorium,
It can be used for components on or in an internal combustion engine such as a diesel soot filter, an automatic catalytic converter, and various exhaust gas filters.

  In the following, the present invention will be described in more detail using the following examples.

Example 1
The method for preparing the coating solution is as follows. That is, 16.6 g of lithium acetate dihydrate, 100 ml of ethanol, 20 g of acetylacetonate, 38 g of zirconium propionate, and 50 ml of ethyl acetate are mixed, and ethanol is added to the resulting mixture to make a total amount of 250 ml.
In the liquid immersion process, a coated glass disk is coated with a coating solution. The coating is carried out at a withdrawal speed of 40 cm / min. The coating layer is then dried at 450 ° C. for 1 hour. This provides the glass disk with friction resistance, long-term stability, and a transparent coating.

Example 2
The method for preparing the coating solution is as follows. That is, 10 g of 1N-HNO ₃ , 20 g of ethanol, 40 ml of lithium nitrate (10% ethanol solution), 40 ml of lithium chloride (10% ethanol solution), and 50 g of SiO _x nanoparticles were mixed, and ethanol was added to make a total amount of 250 ml. To do. In the spraying process, the cleaned glass ceramic plate is coated with a coating solution. The formed coating is translucent.

Example 3
The method for preparing the coating is as follows. That is, 16.6 g of tetraethoxysiloxane was added to 40 g of ethanol that had been charged in advance and stirred, and then 12 ml of hydrochloric acid (concentration 1%) was further added dropwise. After 10 minutes, 7 g of lithium chloride is added to the solution with further stirring. Next, ethanol is added to adjust the total volume of the mixture to 250 ml.
The cleaned glass substrate is immersed in a drawing speed of 20 cm / min. The formed layer is baked for several minutes at 650 ° C. in a tempering step.

Example 4
In addition to the coating liquid treatment, the active surface can be obtained by rubbing the paste. Such coatings are limited to home use. End users can use such pastes to form or retrofit thermal catalytic surfaces.
By adding 25 g of glycerol, 25 g of lithium hydroxystearate (5% aqueous solution), 12.5 g of lithium chloride (25% aqueous solution), and 12.5 g of lithium sulfate (25% aqueous solution) to a blade mixer, the paste was stirred. Prepare. The paste is then thinly processed onto a metal plate with a cloth and rubbed until it is not visible to the eye.

Example 5
A coating solution is prepared through the following steps.
A) First, an amorphous zirconium oxide precursor powder is prepared in order to prepare a coating solution used for coating according to the present invention. For this purpose, for example, 424.9 g of zirconium propionate (■) 77% solution is dropped, 100.1 g of acetylacetone is added, and the mixture is stirred for 25 minutes to generate heat. The lemon yellow solution is stirred for 45 minutes at room temperature and then hydrolyzed with 54.1 g of water. Next, the solvent and other volatile components are removed under conditions of a temperature of 80 ° C. and a pressure of 40 mbar. By this operation, yellow precursor fine powder No. 1 having an oxide content of 51% by weight was obtained. 1 is generated.
Next, a 12% by weight aqueous solution was prepared using this precursor powder. 1 is called.
This stock solution No. 1 is heat-treated at 165 ° C. for 24 hours in an autoclave. Thereby, a stock solution No. 1 containing nanocrystalline ZrO ₂ particles (monoclinic and tetragonal phase) having a particle diameter of 5 to 20 nm dispersed in a colloidal form. 2 is prepared.

B) 23.5 g of ZrO ₂ precursor powder (stock solution No. 1) is dissolved in 363 g of ethanol together with 20 g of lithium acetate dihydrate.
A clean low E glass disk is immersed in the resulting solution, coated onto the immersed disk at a draw rate of 20 cm / min, and then solidified at a firing temperature of 450 ° C.

Example 6
A coating solution is prepared through the following steps.
10.5 g of ZrO ₂ precursor powder (stock solution No. 1 obtained in Example 5A) was added to ZrO ₂ stock solution No. 2 (Example 5A) 45 g and 8.3 g of lithium chloride are dissolved in 150 g of ethanol.
The immersion coating treatment is performed at a drawing speed of 30 cm / min, and the transparent nanocrystalline layer according to the present invention can be produced by baking at a temperature of 350 ° C.

Example 7
The coating solution described in Example 1 is processed onto a highly porous substrate. This substrate is produced in the ceramization process. Here, an untreated glass powder is processed to an untreated glass substrate by a screen printing process. Next, in the ceramization step, the porous layer is converted and further sintered. The formed surface is highly porous, white, and extremely scratch resistant.
The substrate is immersed in the solution described in Example 1 and then dried. The substrate surface maintains a pure white color even after coating with the coating solution.

Example 8
The coating solution described in Example 1 and the particles were mixed so that the content of the particles was 30% by weight.
The particles were made by first preparing two solutions. For this purpose, 20.4 g of lithium acetate dihydrate was mixed in 20 g of acetic acid and 100 g of ethanol to obtain a solution A. In order to prepare the second solution, 49.2 g of aluminum secondary butoxide was mixed with 50 g of isopropanol to obtain a solution B. Next, Solution A was added to Solution B with stirring, and ethanol was added to make a total volume of 250 ml. After 2 hours, the mixture gelled to give a white gel product, and the gel was dried in three stages: 100 ° C for 16 hours, 400 ° C for 3 hours, and 700 ° C for 3 hours. This gel was finely pulverized with mortar to form fine particles.
The coating solution was processed on a general porous ceramic substrate used for exhaust gas processing, dried, and then fired at 600 ° C. for 2 hours.

Comparative Example 1
The method for preparing the coating solution is as follows. First, 50 g of 1N-HNO ₃ , 40 g of ethanol, 9 g of tetramethylorthosilicate, and 60 g of nanoparticles are mixed, and the total amount of the mixed solution is made up to 1 liter using ethanol, followed by stirring to homogenize. Next, 10.6 g of cobalt nitrate (Co (NO ₃ ) ₂ .6H ₂ O) is added to 500 ml of the solution and stirred.
This coating solution is processed into a glass ceramic sample in an immersion process and then fired at 450 ° C.

Comparative Example 2
The method for preparing the coating solution is as follows. That is, 13.2 g of nickel chloride hexahydrate is dissolved in 70 g of ethanol. Next, 20.8 g of tetramethylorthosilicate, 1 g of HCl, and 50 g of ethanol are added to this solution and stirred. Ethanol is added to the resulting mixture to make the total volume 250 ml.
In the immersion step, the coating solution is processed into a glass ceramic sample and then fired at 450 ° C.

Testing Visually investigated the various coatings and qualitatively evaluated their transparency. The catalytic activity can be evaluated by using soot or oil.

  Various stains were deposited on the coating to examine wrinkle degradation. Candlesticks, soot dispersion, or a mixture of soot and rosin was sprayed onto any coated substrate. In preparing the soot dispersion, a 10% concentration soot dispersion was prepared using Detexa Printex U and ethanol. The cocoon rosin mixture was prepared by mixing the 10% cocoon dispersion and 10% rosin ethanol solution 1: 1.

  After drying the soil, the sample was kept at a temperature of 100-550 ° C. In this test, the temperature evaluation was preferably performed over a range of 300 to 550 ° C. or every 50 ° C. and held for 1 hour. Samples were cooled after being placed at each temperature and visually evaluated. The transparent substrate was further measured with a haze meter and further photographed.

  In the case of uncoated glass discs, complete soot decomposition occurs at 550 ° C. (Table 1). This is due to the thermal decomposition of the organic components. All of the surfaces listed in the examples showed better and faster soot degradation compared to the uncoated control surface and the comparative example using fiber metal.

  In order to examine the catalytic activity for food, one drop of oil was dropped onto the coated substrate and then carbonized by burning in a baking oven at 230 ° C. for 30 minutes using upper and lower heat. Then, to examine the cleaning action, the sample was tempered in an oven at 300 ° C., 400 ° C., and 500 ° C. for 1 hour or 2 hours, and the carbonized state of the sample was visually evaluated.

  This test (Table 2) showed a clear advantage compared to the untreated control. That is, a remarkable cleaning effect was recognized even at 400 ° C. for 1 hour, and the sample was cleaned after 2 hours. Therefore, by using the coating according to the present invention, for example, even if the temperature of the pyrolysis oven is lowered by 100 ° C., it is possible to obtain the same cleaning effect as before. Therefore, energy consumption can be greatly reduced by applying such a coating.

Furthermore, as another method for determining the catalytic action, there is a method of measuring the conversion of CO to CO ₂ . In this method, a reaction stream consisting of 1% CO and 0.5% O _{2 in} helium is produced in 125 mg of glass powder coated with the coating solution of Example 1 at a gas flow rate in the reactant of 183.3 ml / min. Passed through. During the passage of the reaction stream, the temperature of the sample chamber gradually increased to 500 ° C. During the measurement period, the CO ₂ concentration in the gas outlet stream was measured, and the CO conversion rate was evaluated based on the measured value. The temperature drop when 50% of the CO was converted to CO ₂ was 300 ° C.

Claims (17)

The coating comprises at least one lithium compound and a substrate material;
At least one lithium compound is included in the coating in an amount corresponding to 2% by weight or more as lithium ions in a weight ratio to the total weight of the coating;
The coating has no precious metal , and
The pH of the selected lithium compound is 11 or less, and the lithium compound is an inorganic lithium salt such as lithium phosphate, lithium nitride, lithium halide and lithium sulfate, or lithium acetate, lithium succinate tetrahydrate, propionic acid A thermal catalyst coating characterized by being selected from organic lithium compounds such as lithium and lithium carboxylate derivatives . The thermal catalyst coating according to claim 1, wherein a lithium compound is introduced into the substrate material. The substrate material includes at least one inorganic material, and the inorganic material is glass and glass solder, or silicon oxide, titanium oxide, zirconium oxide, aluminum oxide, cerium oxide, iron oxide, tin oxide. things, the thermal catalyst coating according to claim 1 or 2, characterized in that any one selected from the sol-gel matrix comprising a boric acid-based material. The substrate material includes at least one organic compound, and the organic compound is any selected from waxes, polymers, surfactants, carboxylic acids, fatty acids, oils, resins, silicone resins, or mixtures thereof. thermal catalyst coating according to any one of claims 1 to 3, characterized in that. The coating is present in a paste or liquid state containing any thickener selected from xanthan gum, glycerol, poly (ethylene glycol), poly (vinyl alcohol), polyvinyl pyrrolidone, cellulose, cellulose derivatives, or mixtures thereof. The thermal catalyst coating according to any one of claims 1 to 4 , wherein: Thermal catalyst coating according to any one of claims 1 to 5, characterized in that contains particles in said coating. Thermal catalyst coating according to any one of claims 1 to 6, the thickness of the coating is characterized in that it is a 1Nm～10myuemu. The thermal catalyst coating according to any one of claims 1 to 7 , wherein the coating is colorless and / or transparent. Substrate with a thermal catalyst coating according to claim 1. 10. The thermal catalyst according to claim 9 , wherein the substrate is made of any material selected from glass, glass ceramic, fired glass, fired glass ceramic, fired ceramic, ceramic, metal, plastic, or enamel. A substrate with a coating . The substrate having a thermal catalyst coating according to claim 9 or 10 , wherein the substrate is composed of a plane, a three-dimensional shape, or particles. The substrate with a thermal catalyst coating according to any one of claims 9 to 11, wherein a barrier layer is arranged between the substrate and the coating. The substrate having a thermal catalyst coating according to claim 9 , wherein an infrared reflection layer is arranged on the substrate. 14. The substrate with a thermal catalyst coating according to claim 9 , wherein the substrate and the coating are colorless and / or transparent. 15. A substrate having a thermocatalytic coating according to any one of claims 9 to 14 , which comprises a step of dissolving a viscous coating, a step of coating a substrate, and a step of drying the coated substrate. Production method. The method according to claim 15, wherein the substrate is dried within a temperature range of 20 to 750 ° C. A substrate provided with the thermal catalyst coating according to any one of claims 9 to 13 .
Components in or on a chimney, flue stove, chimney inner lining material, chimney flue pipe lining, or chimney filter,
Components in or on heating devices, flue tube linings, or flue tube filters,
Cooking utensils, roasting utensils, baking and grilling utensils, inspection glass, inner lining, exhaust pipe lining, exhaust pipe filters, deep frying pans, microwave ovens, baking sheets, baking molds, reticulated baking grids, barbecue sets, industrial automatics Components in or on bread machine,
Components on the steam ventilation fan hood,
Components on the solar thermal system,
Components on the reactor,
A component on or in a combustion system, and a component on or in an internal combustion engine, a component in an exhaust gas pipe, a vehicle exhaust gas catalytic converter, or a diesel soot filter.